Organic Electroluminescent Materials and Devices

ABSTRACT

Novel organic compounds containing triphenylene and triazine moieties are described. These compounds are expected to improve device performance when they are used in organic electroluminescent devices.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority from U.S. Provisional Patent Application Ser. No. 62/003,266, filed May 27, 2014, the entire contents of which is incorporated herein by reference.

PARTIES TO A JOINT RESEARCH AGREEMENT

The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Regents of the University of Michigan, Princeton University, University of Southern California, and the Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.

FIELD OF THE INVENTION

The present invention relates to novel organic materials useful for charge transport and devices, such as organic light emitting diodes, including the same.

BACKGROUND

Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art.

One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)₃, which has the following structure:

In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.

As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.

As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.

More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

In addition to light emitting compounds, compounds that function as charge transport moieties are important contributors to the performance of OLEDs. Improvements in the properties of these compounds may lead to significant improvements in the characteristics of the OLED. There is a need in the art for novel compounds that improve charge injection, transport properties, and overall device performance of OLEDs. The present invention addresses this unmet need.

SUMMARY OF THE INVENTION

According to an embodiment, a compound is provided having a formula:

wherein G¹ is triphenylene or aza-triphenylene;

wherein G² and G³ are each independently selected from the group consisting of benzene, biphenyl, terphenyl, dibenzofuran, dibenzothiophene, dibenzoselenophene, naphthalene, phenanthrene, benzofuran, benzothiophene, benzoselenophene, pyridine, pyrimidine, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, quinoline, isoquinoline, quinazoline, phenanthroline, and combinations thereof;

wherein L¹, L² and L³ are each independently selected from a group consisting of a direct bond, benzene, biphenyl, pyridine, pyramidine, phenylpyridine, and diphenylpyridine;

wherein G¹, G² and G³, are each independently optionally further substituted with one or more substituents selected from the group consisting of deuterium, alkyl, alkoxyl, cycloalkyl, cycloalkoxyl, halogen, nitro, nitrile, silyl, benzene, biphenyl, terphenyl, naphthalene, phenanthrene, and combinations thereof;

wherein L¹, L² and L³ are each independently optionally further substituted with one or more substituents selected from the group consisting of deuterium, alkyl, alkoxyl, cycloalkyl, cycloalkoxyl, halogen, nitro, nitrile, silyl, benzene, biphenyl, terphenyl, naphthalene, phenanthrene, and combinations thereof; and

wherein at least one of L²-G² and L³-G³ has more than six carbon atoms.

In one embodiment, both L²-G² and L³-G³ have more than six carbon atoms. In another embodiment, at least one of L²-G² and L³-G³ has at least twelve carbon atoms.

In one embodiment, G¹ is selected from the group consisting of:

In one embodiment, G¹ has no further substitution.

In one embodiment, the compound has the formula:

In one embodiment, G² and G³ are each independently selected from the group consisting of benzene, biphenyl, terphenyl, naphthalene, phenanthrene, pyridine, pyrimidine, quinoline, isoquinoline, phenanthroline, and combinations thereof. In another embodiment, G² and G³ are each independently selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and combinations thereof.

In one embodiment, G² and G³ are each independently selected from the group consisting of:

In one embodiment, G² and G³ are each independently selected from the group consisting of:

and wherein X is selected from the group consisting of O, S and Se.

In one embodiment, L¹, L² and L³ are each independently selected from the group consisting of: direct bond,

In one embodiment, the compound is selected from the group consisting of Compound 1 to Compound 98.

According to another embodiment, a first device comprising a first organic light emitting device is also provided. The first organic light emitting device can include an anode, a cathode, and an organic layer, disposed between the anode and the cathode. The organic layer can include a compound of Formula I. The first device can be a consumer product, an organic light-emitting device, an electronic component module, and/or a lighting panel.

In one embodiment, the first device is selected from the group consisting of a consumer product, an electronic component module, an organic light-emitting device, and a lighting panel. In another embodiment, the organic layer is an emissive layer and the compound is a host. In another embodiment, the organic layer is a blocking layer and the compound is a blocking material in the organic layer.

In one embodiment, the organic layer further comprises a phosphorescent emissive dopant, wherein the phosphorescent emissive dopant is a transition metal complex having at least one ligand or part of the ligand if the ligand is more than bidentate selected from the group consisting of:

wherein each X¹ to X¹³ are independently selected from the group consisting of carbon and nitrogen;

wherein X is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″;

wherein R′ and R″ are optionally fused or joined to form a ring;

wherein each R_(a), R_(b), R_(c), and R_(d) may represent from mono substitution to the possible maximum number of substitution, or no substitution;

wherein R′, R″, R_(a), R_(b), R_(c), and R_(d) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

wherein any two adjacent substitutents of R_(a), R_(b), R_(c), and R_(d) are optionally fused or joined to form a ring or form a multidentate ligand.

In one embodiment, at least one of R_(a), R_(b), R_(c), and R_(d) is selected from the group consisting of alkyl, cycloalkyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof.

According to another embodiment, a formulation comprising a compound of Formula I is also provided.

In one embodiment, the formulation further comprises a second compound, wherein the second compound is a phosphorescent emissive Ir complex having at least one substituent selected from the group consisting of alkyl, cycloalkyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 which is incorporated by reference in its entirety.

FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 which is incorporated by reference in its entirety.

More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.

Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones, tablets, phablets, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.

The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.

The term “halo,” “halogen,” or “halide” as used herein includes fluorine, chlorine, bromine, and iodine.

The term “alkyl” as used herein contemplates both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like. Additionally, the alkyl group may be optionally substituted.

The term “cycloalkyl” as used herein contemplates cyclic alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 7 carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.

The term “alkenyl” as used herein contemplates both straight and branched chain alkene radicals. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl group may be optionally substituted.

The term “alkynyl” as used herein contemplates both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.

The terms “aralkyl” or “arylalkyl” as used herein are used interchangeably and contemplate an alkyl group that has as a substituent an aromatic group. Additionally, the aralkyl group may be optionally substituted.

The term “heterocyclic group” as used herein contemplates aromatic and non-aromatic cyclic radicals. Hetero-aromatic cyclic radicals also means heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 or 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperdino, pyrrolidino, and the like, and cyclic ethers, such as tetrahydrofuran, tetrahydropyran, and the like. Additionally, the heterocyclic group may be optionally substituted.

The term “aryl” or “aromatic group” as used herein contemplates single-ring groups and polycyclic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is aromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Additionally, the aryl group may be optionally substituted.

The term “heteroaryl” as used herein contemplates single-ring hetero-aromatic groups that may include from one to three heteroatoms, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine and pyrimidine, and the like. The term heteroaryl also includes polycyclic hetero-aromatic systems having two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Additionally, the heteroaryl group may be optionally substituted.

The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl may be optionally substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof

As used herein, “substituted” indicates that a substituent other than H is bonded to the relevant position, such as carbon. Thus, for example, where R¹ is mono-substituted, then one R¹ must be other than H. Similarly, where R¹ is di-substituted, then two of R¹ must be other than H. Similarly, where R¹ is unsubstituted, R¹ is hydrogen for all available positions.

The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective fragment can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.

It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.

In one aspect, the compounds of the invention contain both a triphenylene or aza-triphenylene ring and a triazine ring. These compounds provide a new type of material which may be advantageously used in OLEDs. The triphenylene moiety and its analogues are excellent charge transport moieties due to their rigid disk-shape chemical structures, which benefits molecular assembly. The triazine moiety has a deep LUMO level that enables efficient electron injection from adjacent layers. Compounds with this unique combination of rings further improve charge injection and transport properties of OLEDs, thus improving overall device performance. These compounds may be used as non-emitting materials in a device. In one embodiment, these compounds may be used as a host in the emissive layer of an OLED. In another embodiment, these compounds may be used as a host in the emissive layer of a phosphorescent OLED. These compounds may also be used as materials in a variety of other non-emissive layers within the device structure, such as a hole blocking material within a hole blocking layer.

Compounds of the Invention:

The compounds of the present invention may be synthesized using techniques well-known in the art of organic synthesis. The starting materials and intermediates required for the synthesis may be obtained from commercial sources or synthesized according to methods known to those skilled in the art.

In one aspect, the compound of the invention is a compound having a formula:

wherein G¹ is triphenylene or aza-triphenylene;

wherein G² and G³ are each independently selected from the group consisting of benzene, biphenyl, terphenyl, dibenzofuran, dibenzothiophene, dibenzoselenophene, naphthalene, phenanthrene, benzofuran, benzothiophene, benzoselenophene, pyridine, pyrimidine, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, quinoline, isoquinoline, quinazoline, phenanthroline, and combinations thereof;

wherein L¹, L² and L³ are each independently selected from a group consisting of a direct bond, benzene, biphenyl, pyridine, pyramidine, phenylpyridine, and diphenylpyridine;

wherein G¹, G² and G³, are each independently optionally further substituted with one or more substituents selected from the group consisting of deuterium, alkyl, alkoxyl, cycloalkyl, cycloalkoxyl, halogen, nitro, nitrile, silyl, benzene, biphenyl, terphenyl, naphthalene, phenanthrene, and combinations thereof;

wherein L¹, L² and L³ are each independently optionally further substituted with one or more substituents selected from the group consisting of deuterium, alkyl, alkoxyl, cycloalkyl, cycloalkoxyl, halogen, nitro, nitrile, silyl, benzene, biphenyl, terphenyl, naphthalene, phenanthrene, and combinations thereof; and

wherein at least one of L²-G² and L³-G³ has more than six carbon atoms.

G¹ may be any triphenylene or aza-triphenylene ring, as would be understood by one of ordinary skill in the art. In one embodiment, G¹ is selected from the group consisting of:

The structures of each of G² and G³ are not particularly limited. In one embodiment, G² and G³ are each a ring. In one embodiment, G² and G³ are each independently selected from the group consisting of an aryl ring and a heteroaryl ring.

In one embodiment, G² and G³ are each independently selected from the group consisting of benzene, biphenyl, terphenyl, naphthalene, phenanthrene, pyridine, pyrimidine, quinoline, isoquinoline, phenanthroline, and combinations thereof. In another embodiment, G² and G³ are each independently selected from the group consisting of:

In one embodiment, G² and G³ are each independently selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and combinations thereof. In another embodiment, G² and G³ are each independently selected from the group consisting of:

and wherein X is selected from the group consisting of 0, S and Se.

In some embodiments, G¹, G², and G³ are each independently optionally substituted with one, two three, four, five, six, seven, eight, nine, or ten or more substituents. In one embodiment, the substituent is selected from the group consisting of deuterium, alkyl, alkoxyl, cycloalkyl, cycloalkoxyl, halogen, nitro, nitrile, silyl, benzene, biphenyl, terphenyl, naphthalene, phenanthrene, and combinations thereof. In one embodiment, at least one of G¹, G², and G³ is substituted with at least one halogen. In other embodiments, at least one of G¹, G², and G³ has no further substitution. In one embodiment, G¹ has no further substitution. In another embodiment, G² has no further substitution. In another embodiment, G³ has no further substitution.

L¹, L² and L³ are each not particularly limited. In one embodiment, at least one of L¹, L² or L³ is a direct bond. In another embodiment, at least one of L¹, L² or L³ is an alkyl group. In another embodiment, at least one of L¹, L² or L³ is a ring. In another embodiment, L¹, L² and L³ are each independently selected from the group consisting of a direct bond and a ring. In one embodiment, the ring is an aryl ring or a heteroaryl ring. In another embodiment, L¹, L² and L³ are each independently selected from a group consisting of a direct bond, benzene, biphenyl, pyridine, pyramidine, phenylpyridine, and diphenylpyridine. In another embodiment, L¹, L² and L³ are each independently selected from the group consisting of: direct bond,

In some embodiments, L¹, L² and L³ are each independently optionally substituted with one, two three, four, five, six, seven, or eight or more substituents. In one embodiment, L¹, L² and L³ are each independently optionally further substituted with one or more substituents selected from the group consisting of deuterium, alkyl, alkoxyl, cycloalkyl, cycloalkoxyl, halogen, nitro, nitrile, silyl, benzene, biphenyl, terphenyl, naphthalene, phenanthrene, and combinations thereof. In one embodiment, L¹ has no further substitution. In another embodiment, L² has no further substitution. In another embodiment, L³ has no further substitution.

The total number of carbon atoms of each of L²-G² and L³-G³ is not particularly limited, as long as at least one of L²-G² and L³-G³ has more than six carbon atoms. In one embodiment, at least one of L²-G² and L³-G³ has more than six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, or sixteen or more carbon atoms. In one embodiment, at least one of L²-G² and L³-G³ has more than six carbon atoms. In another embodiment, both L²-G² and L³-G³ have more than six carbon atoms. In another embodiment, at least one of L²-G² and L³-G³ has at least twelve carbon atoms. In another embodiment, both L²-G² and L³-G³ have more than twelve carbon atoms.

In one embodiment, the compound has the formula:

In one embodiment, the compound is selected from the group consisting of Compound 1 to Compound 98:

In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.

Devices:

According to another aspect of the present disclosure, a first device is also provided. The first device includes a first organic light emitting device, that includes an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer may include a host and a phosphorescent dopant. The emissive layer can include a compound of Formula I, and its variations as described herein.

The first device can be one or more of a consumer product, an electronic component module, an organic light-emitting device and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments. The organic layer can be an emissive layer and the compound can be a host in some embodiments. The organic layer can be a charge transporting layer and the compound can be a charge transporting material in the organic layer in some embodiments. The organic layer can be a blocking layer and the compound can be a blocking material in the organic layer in some embodiments.

In one embodiment, the organic layer further comprises a phosphorescent emissive dopant, wherein the phosphorescent emissive dopant is a transition metal complex having at least one ligand or part of the ligand if the ligand is more than bidentate selected from the group consisting of:

wherein each X¹ to X¹³ are independently selected from the group consisting of carbon and nitrogen;

wherein X is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″;

wherein R′ and R″ are optionally fused or joined to form a ring;

wherein each R_(a), R_(b), R_(c), and R_(d) may represent from mono substitution to the possible maximum number of substitution, or no substitution;

wherein R′, R″, R_(a), R_(b), R_(c), and R_(d) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

wherein any two adjacent substitutents of R_(a), R_(b), R_(c), and R_(d) are optionally fused or joined to form a ring or form a multidentate ligand.

In one embodiment, at least one of R_(a), R_(b), R_(c), and R_(d) is selected from the group consisting of alkyl, cycloalkyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof.

The organic layer can also include a host. In some embodiments, the host can include a metal complex. The host can be a triphenylene containing benzo-fused thiophene or benzo-fused furan. Any substituent in the host can be an unfused substituent independently selected from the group consisting of C—H_(2n+1), OC_(n)H_(2n+1), OAr₁, N(C_(n)H_(2n+1))₂, N(Ar₁)(Ar₂), CH═CH—C—H_(2m+1), C≡C—C_(n)H_(2n+1), Ar₁, Ar₁-Ar₂, and C—H_(2n)—Ar₁, or no substitution. In the preceding substituents n can range from 1 to 10; and Ar₁ and Ar₂ can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof

The host can be a compound comprising at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. The host can include a metal complex. The host can be a specific compound selected from the group consisting of:

and combinations thereof

Formulations:

In yet another aspect of the present disclosure, a formulation that comprises a compound of Formula I is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, and an electron transport layer material, disclosed herein. In one embodiment, the formulation further comprises a second compound; wherein the second compound is a phosphorescent emissive Ir complex having at least one substituent selected from the group consisting of alkyl, cycloalkyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof.

Combination with Other Materials

The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

HIL/HTL:

A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoO_(x); a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and cross-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include, but are not limited to the following general structures:

Each of Ar¹ to Ar⁹ is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each Ar is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, Ar¹ to Ar⁹ is independently selected from the group consisting of:

wherein k is an integer from 1 to 20; X¹⁰¹ to X¹⁰⁸ is C (including CH) or N; Z¹⁰¹ is NAr¹, O, or S; Ar¹ has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:

wherein Met is a metal, which can have an atomic weight greater than 40; (Y¹⁰¹-Y¹⁰²) is a bidentate ligand, Y¹⁰¹ and Y¹⁰² are independently selected from C, N, O, P, and S; L¹⁰¹ is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.

In one aspect, (Y¹⁰¹-Y¹⁰²) is a 2-phenylpyridine derivative. In another aspect, (Y¹⁰¹-Y¹⁰²) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc⁺/Fc couple less than about 0.6 V.

Host:

The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criteria is satisfied.

Examples of metal complexes used as host are preferred to have the following general formula:

wherein Met is a metal; (Y¹⁰³-Y¹⁰⁴) is a bidentate ligand, Y¹⁰³ and Y¹⁰⁴ are independently selected from C, N, O, P, and S; L¹⁰¹ is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.

In one aspect, the metal complexes are:

wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.

In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y¹⁰³-Y¹⁰⁴) is a carbene ligand.

Examples of organic compounds used as host are selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, the host compound contains at least one of the following groups in the molecule:

wherein R¹⁰¹ to R¹⁰⁷ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 0 to 20 or 1 to 20; k′ is an integer from 0 to 20. X¹⁰¹ to X¹⁰⁸ is selected from C (including CH) or N. Z¹⁰¹ and Z¹⁰² is selected from NR¹⁰¹, O, or S.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED.

In one aspect, the compound used in the HBL contains the same molecule or the same functional groups used as the host described above.

In another aspect, the compound used in the HBL contains at least one of the following groups in the molecule:

wherein k is an integer from 1 to 20; L¹⁰¹ is an another ligand, k′ is an integer from 1 to 3.

ETL:

Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.

In one aspect, the compound used in ETL contains at least one of the following groups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar¹ to Ar³ has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X¹⁰¹ to X¹⁰⁸ is selected from C (including CH) or N.

In another aspect, the metal complexes used in ETL contains, but is not limited to, the following general formula:

wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L¹⁰¹ is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.

In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.

In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exiton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED. Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in Table A below. Table A lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.

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EXPERIMENTAL

Synthesis of Exemplary Compounds of the Invention

Chemical abbreviations used throughout are as follows:

-   -   SPhos is         dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine         Pd₂(dba)₃ is tri(dibenzylideneacetone) dipalladium(0),     -   Pd(PPh₃)₄ is tetrakis(triphenylphosphine) palladium(0),     -   DCM is dichloromethane,     -   EtOAc is ethyl acetate,     -   DME is dimethyoxyethane, and     -   THF is tetrahydrofuran.

Compound 2

Triphenylen-2-ylboronic acid (4.20 g, 15.4 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (3.49 g, 15.4 mmol), and Pd(PPh₃)₄ (0.89 g, 0.77 mmol) were added to THF (200 ml) with a 2 M aqueous K₂CO₃ solution (23.2 ml, 46.3 mmol). The reaction mixture was degassed thoroughly and heated to reflux under nitrogen for 16 h. After cooling to room temperature, the solid was collected by filtration, washed with THF and heptane to give 2-chloro-4-phenyl-6-(triphenylen-2-yl)-1,3,5-triazine (3.7 g, 57%) as a pale yellow solid. The product was used without further purification.

A solution of 2-chloro-4-phenyl-6-(triphenylen-2-yl)-1,3,5-triazine (3.7 g, 8.9 mmol), [1,1′-biphenyl]-4-ylboronic acid (2.6 g, 13.3 mmol), Pd(PPh₃)₄ (0.51 g, 0.44 mmol), and potassium carbon (K₂CO₃) (3.7 g, 26.6 mmol) in toluene (100 ml), DME (100 ml), and water (20 ml) was refluxed under nitrogen for 16 h. After cooling to room temperature, the solid was collected by filtration, washed with water and toluene, re-dissolved in boiling o-xylene, and filtered through a short plug of silica gel. Upon evaporation of the solvent, the crude product was recrystallized from o-xylene to give Compound 2 (4.5 g, 95%) as a white solid.

Compound 3

A solution of triphenylen-2-ylboronic acid (2.18 g, 8.00 mmol), 2,4-di([1,1′-biphenyl]-4-yl)-6-chloro-1,3,5-triazine (2.80 g, 6.67 mmol), Pd(PPh₃)₄ (0.31 g, 0.27 mmol) and K₂CO₃ (2.76 g, 20.00 mmol) in DME (80 ml), toluene (120 ml) and water (20 ml) was refluxed under nitrogen for 4 h. After cooling to room temperature, the reaction mixture was diluted with water. The solid was collected by filtration, washed with ethanol, re-dissolved in boiling toluene, and filtered through a short plug of silica gel. Upon evaporation off the solvent, the crude product was recrystallized from toluene to yield Compound 3 (3.50 g, 86%) as a white solid.

Compound 5

A solution of [1,1′-biphenyl]-3-ylmagnesium bromide prepared by refluxing 3-bromo-1,1′-biphenyl (10.73 ml, 64.3 mmol) and Mg (4.69 g, 193 mmol) in THF (20 ml) for 2 h was added dropwise to a solution of 2,4,6-trichloro-1,3,5-triazine (3.96 g, 21.45 mmol) in THF (80 ml) at 0° C. The reaction mixture was gradually warmed to room temperature, stirred for 16 h and quenched with 10% HCl aqueous solution. It was extracted with DCM, washed with water and dried over sodium sulfate (Na₂SO₄). Upon evaporation off the solvent, the crude product was purified by column chromatography on silica gel with heptane/DCM (9/1 to 7/3, v/v) as eluent to yield 2,4-di([1,1′-biphenyl]-3-yl)-6-chloro-1,3,5-triazine (2.30 g, 65%) as a white solid.

A solution of 4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane (2.53 g, 7.14 mmol), 2,4-di([1,1′-biphenyl]-3-yl)-6-chloro-1,3,5-triazine (2.50 g, 5.95 mmol), Pd(PPh₃)₄ (0.69 g, 0.60 mmol) and K₂CO₃ (1.65 g, 11.91 mmol) in DME (100 ml), toluene (100 ml), and water (10 ml) was refluxed under nitrogen for 16 h. After cooling to room temperature, the reaction mixture was diluted with water. The solid was collected by filtration, washed with water, ethanol and toluene, re-dissolved in boiling toluene and filtered through a short plug of silica gel. Upon evaporation of the solvent, Compound 5 (2.70 g, 74%) was recrystallized from toluene as a white solid.

Compound 6

A solution of 2-chloro-4-phenyl-6-(triphenylen-2-yl)-1,3,5-triazine (3.9 g, 9.33 mmol), 2-([1,1′:4′,1″-terphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.99 g, 11.20 mmol), Pd(PPh₃)₄ (0.539 g, 0.467 mmol) and K₂CO₃ (3.87 g, 28.0 mmol) in toluene (100 ml), DME (100 ml), and water (20.00 ml) was refluxed under nitrogen for 16 h. After cooling to room temperature, the solid was collected by filtration, washed with water and toluene, dissolved in boiling xylene and filtered through a short plug of silica gel. Upon evaporation of the solvent, Compound 6 (4.9 g, 86%) was recrystallized from xylene to give a white solid.

Compound 21

A solution of 4,4,5,5-tetramethyl-2-(3-(triphenylen-2-yl)phenyl)-1,3,2-dioxaborolane (3.76 g, 8.73 mmol), 2-([1,1′-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (2.5 g, 7.27 mmol), Pd(PPh₃)₄ (0.420 g, 0.364 mmol), and K₂CO₃ (2.010 g, 14.54 mmol) in toluene (100 ml), DME (100 ml), and water (10 ml) was refluxed under nitrogen for 16 h. After cooling to room temperature, the solid was collected by filtration, dissolved in boiling toluene, filtered through a short plug of silica gel and recrystallized from toluene to yield Compound 21 (3 g, 67.4%) as a white solid.

Compound 32

A solution of 4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane (2.345 g, 6.62 mmol), 2-chloro-4-(dibenzo[b,d]thiophen-4-yl)-6-phenyl-1,3,5-triazine (2.25 g, 6.02 mmol), Pd(PPh₃)₄ (0.348 g, 0.301 mmol), and potassium carbonate (2.495 g, 18.05 mmol) in DME (54.7 ml) and water (5.47 ml) was refluxed under nitrogen for 16 h. After cooling to room temperature, the solid was collected by filtration, washed successively with THF, water and ethanol, and triturated with boiling ethanol to yield Compound 32 (3.3 g, 80%) as a white solid.

Compound 50

A suspension of 2-chloro-4-phenyl-6-(triphenylen-2-yl)-1,3,5-triazine (2.5 g, 5.98 mmol), 2-(3-(dibenzo[b,d]thiophen-4-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.311 g, 5.98 mmol), Pd(PPh₃)₄ (0.138 g, 0.120 mmol) and K₂CO₃ (2.480 g, 17.95 mmol) in toluene (200 ml), DME (10 ml), and water (15 ml) was refluxed under nitrogen for 16 h. After cooling to room temperature, the reaction mixture was diluted with water and the solid was collected by filtration, and washed successively with ethanol, water, DCM and hot toluene. The crude product was triturated with boiling DCM to yield Compound 50 (3.2 g, 83%) as a white solid.

Compound 53

A solution of 2-chloro-4-phenyl-6-(triphenylen-2-yl)-1,3,5-triazine (4.63 g, 11.09 mmol), 2-(dibenzo[b,d]thiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.3 g, 13.86 mmol), Pd(PPh₃)₄ (0.801 g, 0.693 mmol), and K₂CO₃ (5.75 g, 41.6 mmol) in toluene (200 ml), DME (200 ml), and water (40.0 ml) was refluxed under nitrogen for 16 h. After cooling to room temperature, the solid was collected by filtration, washed successively with water and toluene, dissolved in boiling xylene, passed through a short plug of silica gel and recrystallized from xylene to yield Compound 53 (5.3 g, 68%) as a white solid.

Compound 80

A solution of 2-chloro-4-(dibenzo[b,d]thiophen-4-yl)-6-phenyl-1,3,5-triazine (2.5 g, 6.69 mmol), 4,4,5,5-tetramethyl-2-(3-(triphenylen-2-yl)phenyl)-1,3,2-dioxaborolane (3.17 g, 7.36 mmol), Pd(PPh₃)₄ (0.386 g, 0.334 mmol), and K₂CO₃ (2.77 g, 20.06 mmol) in DME (40.1 ml) and water (13.37 ml) was refluxed under nitrogen for 16 h. After cooling to room temperature, the solid was collected by filtration, washed with water and ethanol, triturated with boiling ethanol and recrystallized from toluene to yield Compound 80 (2.5 g, 58%) as a white solid.

Device Examples

All OLED devices were fabricated by high vacuum (˜10⁻⁷ Torr) thermal evaporation. The anode electrode was 120 nm of indium tin oxide (ITO). The cathode electrode consisted of 1 nm of LiF followed by 100 nm of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H₂O and O₂) immediately after fabrication, and a moisture getter was incorporated inside the package.

A first set of device examples have organic stacks consisting of, sequentially, from the ITO surface, 10 nm of LG101 (from LG Chem) as the hole injection layer (HIL), 45 nm of 4,4′-bis[N-(1-naphthyl)-N-phenylaminolbiphenyl (NPD) as the hole-transport layer (HTL), and 40 nm of emissive layer (EML). On top of the EML, 5 nm of inventive compounds or comparative compounds was deposited as the hole blocking layer (HBL), followed by 40 nm of tris(8-hydroxyquinolinato)aluminum (Alq₃) as the electron-transport layer (ETL). The EML consists of two components: 90 wt % of inventive compound or comparative compound is used as the host, with 10 wt % of GD as emissive dopant. The structures of the compounds used are shown below.

Table 1 is a summary of the device data recorded at 1000 nits. LT95 is defined as the time it takes to decay to 95% of the initial luminance at a constant current density and is normalized to that of Device C-1.

Emission LE LT95 Device Host HBL Color [cd/A] [A.U.] C-1 CC-1 CC-1 Green 50 100 1 Compound 5 Compound 5 Green 60 204 2 Compound 6 Compound 6 Green 50 351 3 Compound 21 Compound 21 Green 57 519 4 Compound 50 Compound 50 Green 51 577 5 Compound 53 Compound 53 Green 56 161

All of the first set of devices emit green color, consistent with the emission feature of the dopant GD. Devices 1, 2, 3, 4 and 5, which use inventive compounds as HBL and host in EML, have equivalent or higher efficiency and longer lifetime than Device C-1, which uses comparative compound. According to the device data, the inventive compounds having biphenyl, terphenyl or dibenzothiophene moiety attached to triazine core seem to be superior to the compound containing two benzene moieties.

A second set of devices were fabricated with the same structure as the first set of devices except that the EML in the second set of the devices has three components: 70 wt % of HH is used as the host, with 20 wt % of inventive compounds (Compounds 6, 21 and 32) or comparative compound (CC-2) as co-host, and 10 wt % of GD as emissive dopant. The chemical structures of the compounds used are presented below:

Table 2 is a summary of the device data recorded at 1000 nits. LT95 is defined as the time it takes to decay to 95% of the initial luminance at a constant current density and is normalized to that of Device C-2.

Emission LE LT95 Device Co-host HBL Color [cd/A] [A.U.] C-2 CC-2 CC-2 Green 56 100 6 Compound 6 Compound 6 Green 64 231 7 Compound 21 Compound 21 Green 64 378 8 Compound 32 Compound 32 Green 56 125

All of the second set of devices emit green color, consistent with the emission feature of the dopant GD. Devices 6, 7 and 8, which use inventive compounds as HBL and co-host in EML, have equivalent or higher efficiency and longer lifetime than Device C-2, which uses comparative compounds. According to the device data, the inventive compounds having biphenyl, terphenyl or dibenzothiophene moiety attached to the triazine core are superior to the compound containing a fluorene moiety.

It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.

The disclosures of each and every patent, patent application, and publication cited herein are hereby incorporated herein by reference in their entirety. While this invention has been disclosed with reference to specific embodiments, it is apparent that other embodiments and variations of this invention may be devised by others skilled in the art without departing from the true spirit and scope of the invention. The appended claims are intended to be construed to include all such embodiments and equivalent variations. 

We claim:
 1. A compound having a formula:

wherein G¹ is triphenylene or aza-triphenylene; wherein G² and G³ are each independently selected from the group consisting of benzene, biphenyl, terphenyl, dibenzofuran, dibenzothiophene, dibenzoselenophene, naphthalene, phenanthrene, benzofuran, benzothiophene, benzoselenophene, pyridine, pyrimidine, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, quinoline, isoquinoline, quinazoline, phenanthroline, and combinations thereof; wherein L¹, L² and L³ are each independently selected from a group consisting of a direct bond, benzene, biphenyl, pyridine, pyramidine, phenylpyridine, and diphenylpyridine; wherein G¹, G² and G³, are each independently optionally further substituted with one or more substituents selected from the group consisting of deuterium, alkyl, alkoxyl, cycloalkyl, cycloalkoxyl, halogen, nitro, nitrile, silyl, benzene, biphenyl, terphenyl, naphthalene, phenanthrene, and combinations thereof; wherein L¹, L² and L³ are each independently optionally further substituted with one or more substituents selected from the group consisting of deuterium, alkyl, alkoxyl, cycloalkyl, cycloalkoxyl, halogen, nitro, nitrile, silyl, benzene, biphenyl, terphenyl, naphthalene, phenanthrene, and combinations thereof; and wherein at least one of L²-G² and L³-G³ has more than six carbon atoms.
 2. The compound of claim 1, wherein both L²-G² and L³-G³ have more than six carbon atoms.
 3. The compound of claim 1, wherein at least one of L²-G² and L³-G³ has at least twelve carbon atoms.
 4. The compound of claim 1, wherein G¹ is selected from the group consisting of:


5. The compound of claim 1, wherein G¹ has no further substitution.
 6. The compound of claim 1, wherein the compound has the formula:


7. The compound of claim 1, wherein G² and G³ are each independently selected from the group consisting of benzene, biphenyl, terphenyl, naphthalene, phenanthrene, pyridine, pyrimidine, quinoline, isoquinoline, phenanthroline, and combinations thereof.
 8. The compound of claim 1, wherein G² and G³ are each independently selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and combinations thereof.
 9. The compound of claim 1, wherein G² and G³ are each independently selected from the group consisting of:


10. The compound of claim 1, wherein G² and G³ are each independently selected from the group consisting of:

and wherein X is selected from the group consisting of O, S and Se.
 11. The compound of claim 1, wherein L¹, L² and L³ are each independently selected from the group consisting of: direct bond,


12. The compound of claim 1, wherein the compound is selected from the group consisting of Compound 1 to Compound 98:


13. A first device comprising a first organic light emitting device, the first organic light emitting device comprising: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound having a formula:

wherein G¹ is triphenylene or aza-triphenylene; wherein G² and G³ are each independently selected from the group consisting of benzene, biphenyl, terphenyl, dibenzofuran, dibenzothiophene, dibenzoselenophene, naphthalene, phenanthrene, benzofuran, benzothiophene, benzoselenophene, pyridine, pyrimidine, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, quinoline, isoquinoline, quinazoline, phenanthroline, and combinations thereof; wherein L¹, L² and L³ are each independently selected from a group consisting of a direct bond, benzene, biphenyl, pyridine, pyramidine, phenylpyridine, and diphenylpyridine; wherein G¹, G² and G³, are each independently optionally further substituted with one or more substituents selected from the group consisting of deuterium, alkyl, alkoxyl, cycloalkyl, cycloalkoxyl, halogen, nitro, nitrile, silyl, benzene, biphenyl, terphenyl, naphthalene, phenanthrene, and combinations thereof; wherein L¹, L² and L³ are each independently optionally further substituted with one or more substituents selected from the group consisting of deuterium, alkyl, alkoxyl, cycloalkyl, cycloalkoxyl, halogen, nitro, nitrile, silyl, benzene, biphenyl, terphenyl, naphthalene, phenanthrene, and combinations thereof; and wherein at least one of L²-G² and L³-G³ has more than six carbon atoms.
 14. The first device of claim 13, wherein the organic layer is an emissive layer and the compound is a host.
 15. The first device of claim 13, wherein the organic layer further comprises a phosphorescent emissive dopant, wherein the phosphorescent emissive dopant is a transition metal complex having at least one ligand or part of the ligand if the ligand is more than bidentate selected from the group consisting of:

wherein each X¹ to X¹³ are independently selected from the group consisting of carbon and nitrogen; wherein X is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; wherein R′ and R″ are optionally fused or joined to form a ring; wherein each R_(a), R_(b), R_(c), and R_(d) may represent from mono substitution to the possible maximum number of substitution, or no substitution; wherein R′, R″, R_(a), R_(b), R_(c), and R_(d) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any two adjacent substitutents of R_(a), R_(b), R_(c), and R_(d) are optionally fused or joined to form a ring or form a multidentate ligand.
 16. The first device of claim 15, wherein at least one of R_(a), R_(b), R_(c), and R_(d) is selected from the group consisting of alkyl, cycloalkyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof.
 17. The first device of claim 13, wherein the organic layer is a hole blocking layer and the compound is a hole blocking material in the organic layer.
 18. The first device of claim 13, wherein the first device is selected from the group consisting of a consumer product, an electronic component module, an organic light-emitting device, and a lighting panel.
 19. A formulation comprising a first compound having a formula:

wherein G¹ is triphenylene or aza-triphenylene; wherein G² and G³ are each independently selected from the group consisting of benzene, biphenyl, terphenyl, dibenzofuran, dibenzothiophene, dibenzoselenophene, naphthalene, phenanthrene, benzofuran, benzothiophene, benzoselenophene, pyridine, pyrimidine, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, quinoline, isoquinoline, quinazoline, phenanthroline, and combinations thereof; wherein L¹, L² and L³ are each independently selected from a group consisting of a direct bond, benzene, biphenyl, pyridine, pyramidine, phenylpyridine, and diphenylpyridine; wherein G¹, G² and G³, are each independently optionally further substituted with one or more substituents selected from the group consisting of deuterium, alkyl, alkoxyl, cycloalkyl, cycloalkoxyl, halogen, nitro, nitrile, silyl, benzene, biphenyl, terphenyl, naphthalene, phenanthrene, and combinations thereof; wherein L¹, L² and L³ are each independently optionally further substituted with one or more substituents selected from the group consisting of deuterium, alkyl, alkoxyl, cycloalkyl, cycloalkoxyl, halogen, nitro, nitrile, silyl, benzene, biphenyl, terphenyl, naphthalene, phenanthrene, and combinations thereof; and wherein at least one of L²-G² and L³-G³ has more than six carbon atoms.
 20. The formulation of claim 19, wherein the formulation further comprises a second compound; wherein the second compound is a phosphorescent emissive Ir complex having at least one substituent selected from the group consisting of alkyl, cycloalkyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof. 